JP2016027038A - Improved process for selective dimerization of ethylene to 1-butene - Google Patents
Improved process for selective dimerization of ethylene to 1-butene Download PDFInfo
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- JP2016027038A JP2016027038A JP2015132370A JP2015132370A JP2016027038A JP 2016027038 A JP2016027038 A JP 2016027038A JP 2015132370 A JP2015132370 A JP 2015132370A JP 2015132370 A JP2015132370 A JP 2015132370A JP 2016027038 A JP2016027038 A JP 2016027038A
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- titanium compound
- aluminum
- ethylene
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000005977 Ethylene Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 16
- 238000006471 dimerization reaction Methods 0.000 title abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 24
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 45
- 239000010936 titanium Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 150000003609 titanium compounds Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000447 dimerizing effect Effects 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims 2
- OKAMTPRCXVGTND-UHFFFAOYSA-N 2-methoxyoxolane Chemical compound COC1CCCO1 OKAMTPRCXVGTND-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、エチレンの1−ブテンへの選択的ダイマー化に関する。本発明の一つの目的は、特定の触媒組成物を用いてエチレンをダイマー化させる方法を提供することにある。 The present invention relates to the selective dimerization of ethylene to 1-butene. One object of the present invention is to provide a process for dimerizing ethylene using a specific catalyst composition.
エチレンを1−ブテンに選択的にダイマー化させることができる触媒系の中で、バナジウム(非特許文献1〜2)、鉄またはコバルト(非特許文献3〜4)、タングステン(非特許文献5、R. Toozeら(Sasol Technology)の特許文献1(2005))、タンタル(非特許文献6〜7)、ニッケル(非特許文献8〜12)あるいはTi(非特許文献13)をベースとする触媒系を文献中に確認することが可能である。 Among catalyst systems that can selectively dimerize ethylene to 1-butene, vanadium (Non-patent Documents 1 to 2), iron or cobalt (Non-patent Documents 3 to 4), tungsten (Non-patent Documents 5 and 4, R. Tooze et al. (Sasol Technology) Patent Document 1 (2005)), catalyst systems based on tantalum (Non-Patent Documents 6-7), nickel (Non-Patent Documents 8-12) or Ti (Non-Patent Document 13). Can be confirmed in the literature.
これらの系のうち、チタンをベースとするものが卓越している。特許文献2において、K. Zieglerは、トリアルキルアルミニウムとチタンまたはジルコニウムのテトラアルコラートとを混合することによって得られた触媒を用いてエチレンを1−ブテンにダイマー化させる方法を記載した。反応の間、所定量の高分子質量のポリエチレンも形成される;これは、方法の実施の際にかなりの有害作用を有する。 Of these systems, those based on titanium are outstanding. In Patent Document 2, K. Ziegler described a method of dimerizing ethylene to 1-butene using a catalyst obtained by mixing a trialkylaluminum and a tetraalcolate of titanium or zirconium. During the reaction, a certain amount of high molecular weight polyethylene is also formed; this has considerable detrimental effects in carrying out the process.
ポリエチレンの量を低減させるために複数の改善が、特に、特許文献3〜5において提案された。特許文献3では、触媒の要素と一緒に有機リン化合物を使用することが推奨され、特許文献4には、水素により触媒を処理することが記載され、特許文献5には、反応媒体のための溶媒として種々のエーテルを使用することが記載される。最初の触媒系に対するこれらの改変は、反応の選択性を改善するが、それらは、特に、ほんの痕跡量の極性化合物をブテン中に残す溶媒から1−ブテンが分離されなければならない工業的方法において、ほとんど実用性のないものであることが分かった。 In order to reduce the amount of polyethylene, several improvements have been proposed, especially in US Pat. In Patent Document 3, it is recommended to use an organophosphorus compound together with a catalyst element, Patent Document 4 describes treating the catalyst with hydrogen, and Patent Document 5 describes a reaction medium for the reaction medium. The use of various ethers as a solvent is described. Although these modifications to the initial catalyst system improve the selectivity of the reaction, they are particularly useful in industrial processes where 1-butene must be separated from the solvent leaving only trace amounts of polar compounds in the butene. It turned out to be almost impractical.
この観点から、本出願人の特許文献6により、一方のトリアルキルアルミニウムと他方の化学量論量のチタン酸アルキルおよびエーテルタイプの添加物の事前形成された混合物との相互作用によって得られた触媒を用いるとエチレンの1−ブテンへのダイマー化についてのこのような触媒の活性および選択性が明らかに改善されることが実証された。特許文献6にはまた、チタン酸アルキルに対して10超のモル比で前記エーテルタイプの添加物を使用することは、反応をかなり減速し、より乏しい選択性をもたらすことが教示される。 In this respect, according to the applicant's patent document 6, a catalyst obtained by the interaction of one trialkylaluminum with a pre-formed mixture of the other stoichiometric amount of alkyl titanate and ether type additives. Has been demonstrated to clearly improve the activity and selectivity of such catalysts for dimerization of ethylene to 1-butene. U.S. Patent No. 6,057,096 also teaches that the use of the ether type additive in a molar ratio of greater than 10 to alkyl titanate significantly slows the reaction and results in poorer selectivity.
アルキルアルミニウムとチタン酸アルキルとの間のモル比を高めることが生産性における改善につながることが知られている一方で、特許FR255079(特許文献6)の条件下に、これは、方法の操作性に損害を与えて起こる。ますます大量のポリマーが観察されるからである。 While increasing the molar ratio between alkylaluminum and alkyl titanate is known to lead to improvements in productivity, under the conditions of patent FR255079, this is the operability of the process. It happens with damage. This is because an increasing amount of polymer is observed.
反応温度を上げることも、同じ効果、特に、触媒の安定性における低減およびポリマーの割合における上昇を生じさせる。 Increasing the reaction temperature also causes the same effect, particularly a decrease in the stability of the catalyst and an increase in the proportion of polymer.
1−ブテンの選択的形成のために用いられる、チタンをベースとする触媒系の主な不利益は、それ故に、無視できない量のポリマーの形成である。このポリマー形成は、触媒の迅速な失活および大きくなる操作困難性の源である可能性がある。 The main disadvantage of the titanium-based catalyst system used for the selective formation of 1-butene is therefore the formation of a non-negligible amount of polymer. This polymer formation can be a source of rapid deactivation of the catalyst and increased operational difficulties.
本発明の一つの目的は、低減した、さらにはほぼゼロのポリエチレンの生成で、および大きく改善した操作性でエチレンを1−ブテンに選択的にダイマー化させる方法を提供することにある。 One object of the present invention is to provide a process for the selective dimerization of ethylene to 1-butene with reduced and even near zero polyethylene production and with greatly improved operability.
本発明は、触媒組成物を用いてエチレンを1−ブテンに選択的にダイマー化させる方法であって、該触媒組成物は、少なくとも1種のアルコキシまたはアリールオキシのチタン化合物と、エーテルタイプの化合物から選択される少なくとも1種の添加物と、少なくとも1種のアルミニウム化合物とを含み、添加物とチタン化合物との間のモル比が厳密に10超であり、アルミニウム化合物とアルコキシまたはアリールオキシのチタン化合物との間のモル比が厳密に4超である、方法に関する。 The present invention relates to a method for selectively dimerizing ethylene to 1-butene using a catalyst composition, the catalyst composition comprising at least one alkoxy or aryloxy titanium compound and an ether type compound. At least one additive selected from: and at least one aluminum compound, wherein the molar ratio between the additive and the titanium compound is strictly greater than 10, the aluminum compound and the alkoxy or aryloxy titanium It relates to a process wherein the molar ratio between the compounds is strictly greater than 4.
今や、触媒組成物を用いる方法であって、該触媒組成物は、少なくとも1種のアルコキシまたはアリールオキシのチタン化合物と、エーテルタイプの化合物から選択される少なくとも1種の添加物と、少なくとも1種のアルミニウム化合物とを含み、添加物とアルコキシまたはアリールオキシのチタン化合物との間のモル比が、厳密に10超であり、アルミニウム化合物とアルコキシまたはアリールオキシのチタン化合物との間のモル比が厳密に4超である、方法が、低減した、さらにはゼロのポリエチレン生成に伴い、エチレンの1−ブテンへの選択的ダイマー化についての非常に高い選択性を得るために用いられ得ることが見出された。 There is now a method of using a catalyst composition, the catalyst composition comprising at least one alkoxy or aryloxy titanium compound, at least one additive selected from ether type compounds, and at least one kind. The molar ratio between the additive and the alkoxy or aryloxy titanium compound is strictly greater than 10, and the molar ratio between the aluminum compound and the alkoxy or aryloxy titanium compound is strictly It is found that the process can be used to obtain very high selectivity for the selective dimerization of ethylene to 1-butene with reduced and even zero polyethylene production. It was done.
(発明の詳細な説明)
本明細書の以降および上記において、特に指示のない限り、添加物とチタン化合物との間のモル比は、添加物のモル/チタンのモルで表されることになる。本明細書の以降および上記において、特に指示のない限り、アルミニウム化合物とアルコキシまたはアリールオキシのチタン化合物との間のモル比は、アルミニウムのモル/チタンのモルで表されることになる。
(Detailed description of the invention)
In the rest of this specification and above, unless otherwise indicated, the molar ratio between additive and titanium compound will be expressed in moles of additive / moles of titanium. In the remainder of this specification and above, unless otherwise indicated, the molar ratio between the aluminum compound and the alkoxy or aryloxy titanium compound will be expressed in moles of aluminum / moles of titanium.
本発明は、触媒組成物を用いてエチレンを1−ブテンに選択的にダイマー化させる方法であって、該触媒組成物は、少なくとも1種のアルコキシまたはアリールオキシのチタン化合物と、エーテルタイプの化合物から選択される少なくとも1種の添加物と、少なくとも1種のアルミニウム化合物とを含み、前記添加物とチタン化合物との間のモル比は厳密に10超であり、アルミニウム化合物とアルコキシまたはアリールオキシのチタン化合物と間のモル比は、厳密に4超である、方法に関する。 The present invention relates to a method for selectively dimerizing ethylene to 1-butene using a catalyst composition, the catalyst composition comprising at least one alkoxy or aryloxy titanium compound and an ether type compound. At least one additive selected from: and at least one aluminum compound, wherein the molar ratio between the additive and the titanium compound is strictly greater than 10, and the aluminum compound and the alkoxy or aryloxy The molar ratio with respect to the titanium compound relates to a process that is strictly greater than 4.
有利には、触媒組成物の添加物とアルコキシまたはアリールオキシのチタン化合物との間のモル比は、11〜19の範囲である。 Advantageously, the molar ratio between the catalyst composition additive and the alkoxy or aryloxy titanium compound is in the range of 11-19.
有利には、触媒組成物のアルミニウム化合物とアルコキシまたはアリールオキシのチタン化合物との間のモル比は、5〜15の範囲である。 Advantageously, the molar ratio between the aluminum compound of the catalyst composition and the alkoxy or aryloxy titanium compound is in the range of 5-15.
本発明において用いられるアルコキシチタン化合物は、有利には、一般式[Ti(OR)4]を有し、ここで、Rは、2〜30個の炭素原子を含有する線状または分枝のアルキル基である。基Rは、窒素、リン、硫黄および酸素のヘテロ原子をベースとする置換基を含んでよい。 The alkoxytitanium compounds used in the present invention advantageously have the general formula [Ti (OR) 4 ], where R is a linear or branched alkyl containing 2 to 30 carbon atoms. It is a group. The group R may include substituents based on nitrogen, phosphorus, sulfur and oxygen heteroatoms.
挙げられてよい好ましいアルコキシ基の非限定的な例は、以下を含む:テトラエトキシ、テトライソプロポキシ、テトラ−n−ブトキシ、テトラ−2−エチル−へキシルオキシ。 Non-limiting examples of preferred alkoxy groups that may be mentioned include: tetraethoxy, tetraisopropoxy, tetra-n-butoxy, tetra-2-ethyl-hexyloxy.
本発明において用いられるアリールオキシチタン化合物は、有利には、一般式[Ti(OR’)4]を有し、ここで、R’は、2〜30個の炭素原子を含有する、アルキル、アリールまたはアラルキル基により置換されてもされなくてもよいアリール基である。基R’は、窒素、リン、硫黄および酸素のヘテロ原子をベースとする置換基を含んでよい。 The aryloxytitanium compounds used in the present invention advantageously have the general formula [Ti (OR ′) 4 ], where R ′ is an alkyl, aryl containing 2 to 30 carbon atoms Or an aryl group which may or may not be substituted by an aralkyl group. The group R ′ may comprise substituents based on nitrogen, phosphorus, sulfur and oxygen heteroatoms.
挙げられてよい好ましいアリールオキシ基の非限定的な例は、以下を含む:フェノキシ、2−メチルフェノキシ、2,6−ジメチルフェノキシ、2,4,6−トリメチルフェノキシ、4−メチルフェノキシ、2−フェニルフェノキシ、2,6−ジフェニルフェノキシ、2,4,6−トリフェニルフェノキシ、4−フェニルフェノキシ、2−tert−ブチル−6−フェニルフェノキシ、2,4−ジ−tert−ブチル−6−フェニルフェノキシ、2,6−ジイソプロピルフェノキシ、2,6−ジ−tert−ブチルフェノキシ、4−メチル−2,6−ジ−tert−ブチルフェノキシ、2,6−ジクロロ−4−tert−ブチルフェノキシおよび2,6−ジブロモ−4−tert−ブチルフェノキシ、ビフェノキシ基、ビナフトキシ、1,8−ナフタレン−ジオキシ。 Non-limiting examples of preferred aryloxy groups that may be mentioned include: phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-methylphenoxy, 2- Phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-phenylphenoxy, 2-tert-butyl-6-phenylphenoxy, 2,4-di-tert-butyl-6-phenylphenoxy 2,6-diisopropylphenoxy, 2,6-di-tert-butylphenoxy, 4-methyl-2,6-di-tert-butylphenoxy, 2,6-dichloro-4-tert-butylphenoxy and 2,6 -Dibromo-4-tert-butylphenoxy, biphenoxy group, binaphthoxy, 1,8 Naphthalene - dioxy.
本発明のアルミニウム化合物は、有利には、ヒドロカルビルアルミニウム化合物、トリス(ヒドロカルビル)アルミニウム化合物、塩素含有または臭素含有のヒドロカルビルアルミニウム化合物およびアルミノキサンによって形成される群から選択される。 The aluminum compounds of the invention are advantageously selected from the group formed by hydrocarbyl aluminum compounds, tris (hydrocarbyl) aluminum compounds, chlorine- or bromine-containing hydrocarbyl aluminum compounds and aluminoxanes.
トリス(ヒドロカルビル)アルミニウム化合物および塩素含有または臭素含有のヒドロカルビルアルミニウム化合物は、一般式AlR’’mY3−mによって示され、ここで、R’’は、ヒドロカルビル基、好ましくは1〜6個の炭素原子を含有するアルキルであり、Yは、塩素または臭素原子、好ましくは塩素原子であり、mは、1〜3の数である。 Tris (hydrocarbyl) aluminum compounds and chlorine- or bromine-containing hydrocarbylaluminum compounds are represented by the general formula AlR ″ m Y 3-m , where R ″ is a hydrocarbyl group, preferably 1-6 An alkyl containing a carbon atom, Y is a chlorine or bromine atom, preferably a chlorine atom, and m is a number from 1 to 3;
好ましくは、アルミニウム化合物は、ジクロロエチルアルミニウム(EtAlCl2)、エチルアルミニウムセスキクロリド(Et3Al2Cl3)、クロロジエチルアルミニウム(Et2AlCl)、クロロジイソブチルアルミニウム(i−Bu2AlCl)、トリエチルアルミニウム(AlEt3)、トリプロピルアルミニウム(Al(n−Pr)3)、トリイソブチルアルミニウム(Al(i−Bu)3)によって形成される群から選択される。好ましいアルミニウム化合物は、トリエチルアルミニウム(AlEt3)である。 Preferably, the aluminum compound, dichloroethyl aluminum (EtAlCl 2), ethylaluminum sesquichloride (Et 3 Al 2 Cl 3) , chloro diethylaluminum (Et 2 AlCl), chloro diisobutylaluminum (i-Bu 2 AlCl), triethylaluminum (AlEt 3), tripropyl aluminum (Al (n-Pr) 3 ), is selected from the group formed by triisobutyl aluminum (Al (i-Bu) 3 ). A preferred aluminum compound is triethylaluminum (AlEt 3 ).
本発明の触媒組成物の添加物は、有利には、ジエチルエーテル、ジイソプロピルエーテル、2−メトキシ−2−メチルプロパン、2−メトキシ−2−メチルブタン、2,5−ジヒドロフラン、テトラヒドロフラン、2−メトキシテトラヒドロフラン、2−メチルテトラヒドロフラン、3−メチルテトラヒドロフラン、2,3−ジヒドロピラン、テトラヒドロピラン、1,3−ジオキソラン、1,3−ジオキサン、1,4−ジオキサン、ジメトキシエタン、ジ(2−メトキシエチル)エーテルおよびベンゾフランによって形成される群から選択され、単独でまたは混合物として用いられる。 The additive of the catalyst composition of the present invention is advantageously diethyl ether, diisopropyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2,5-dihydrofuran, tetrahydrofuran, 2-methoxy. Tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di (2-methoxyethyl) Selected from the group formed by ethers and benzofurans, used alone or as a mixture.
本発明による特定の組成物は、チタン化合物が[Ti(OnBu)4]であり、添加物がTHFであり、チタン化合物に対するモル比(THF/Ti)(mol/mol)が厳密に10超、好ましくは11〜19の範囲であり、アルミニウム化合物が、トリエチルアルミニウムであり、チタン化合物に対するモル比(AlEt3/Ti)(mol/mol)が厳密に4超、好ましくは5〜15の範囲である、組成物である。 A specific composition according to the present invention has a titanium compound of [Ti (O n Bu) 4 ], an additive of THF, and a molar ratio (THF / Ti) (mol / mol) to the titanium compound of exactly 10 More preferably in the range of 11-19, the aluminum compound is triethylaluminum, and the molar ratio (AlEt 3 / Ti) (mol / mol) to the titanium compound is strictly more than 4, preferably in the range of 5-15 It is a composition.
(本発明の方法において用いられる触媒組成物の調製方法)
本発明による触媒組成物、すなわち、アルコキシまたはアリールオキシのチタン化合物、エーテルタイプの添加物およびアルミニウム化合物は、溶媒との混合物として用いられてよく、その溶媒は、高純度のまたは混合物としての、脂肪族および脂環式の炭化水素、例えば、ヘキサン、シクロヘキサン、ヘプタン、ブタンまたはイソブタンによって、不飽和炭化水素、例えば、4〜20個の炭素原子を含有する、モノオレフィンまたはジオレフィンによって、芳香族炭化水素、例えば、ベンゼン、トルエン、オルト−キシレン、メシチレン、またはエチルベンゼンによって、または、塩素含有炭化水素、例えば、クロロベンゼンまたはジクロロメタンによって形成される群から選択される。有利には、脂肪族炭化水素、例えば、シクロヘキサンまたはn−ヘプタン、および芳香族炭化水素、例えば、トルエンおよびオルト−キシレンが用いられる。
(Method for preparing catalyst composition used in the method of the present invention)
The catalyst composition according to the invention, i.e. alkoxy or aryloxy titanium compounds, ether type additives and aluminum compounds, may be used as a mixture with a solvent, which is a high-purity or as a mixture of fatty acids. Aromatic and alicyclic hydrocarbons such as hexane, cyclohexane, heptane, butane or isobutane, unsaturated hydrocarbons such as monoolefins or diolefins containing 4 to 20 carbon atoms, aromatic carbonization Selected from the group formed by hydrogen, for example benzene, toluene, ortho-xylene, mesitylene, or ethylbenzene, or by a chlorine-containing hydrocarbon, for example chlorobenzene or dichloromethane. Advantageously, aliphatic hydrocarbons such as cyclohexane or n-heptane, and aromatic hydrocarbons such as toluene and ortho-xylene are used.
本発明の触媒組成物の一つの実施形態によると、アルミニウム化合物は、添加物と、アルコキシまたはアリールオキシのチタン化合物とを含有する溶液に加えられる。添加物と、アルコキシまたはアリールオキシのチタン化合物とは、厳密に10超であるモル比で、好ましくは11〜19の範囲の比で存在し、アルミニウム化合物対チタン化合物のモル比は、厳密に4超であり、好ましくは5〜15の範囲である。 According to one embodiment of the catalyst composition of the present invention, the aluminum compound is added to a solution containing the additive and an alkoxy or aryloxy titanium compound. The additive and the alkoxy or aryloxy titanium compound are present in a molar ratio that is strictly greater than 10, preferably in the range of 11 to 19, and the molar ratio of aluminum compound to titanium compound is strictly 4 It is super, Preferably it is the range of 5-15.
触媒溶液中のチタンの濃度は、有利には、1×10−9〜1mol/Lの範囲、好ましくは1×10−6〜0.5mol/Lの範囲である。 The concentration of titanium in the catalyst solution is advantageously in the range of 1 × 10 −9 to 1 mol / L, preferably in the range of 1 × 10 −6 to 0.5 mol / L.
触媒組成物の成分が混合される場所の温度は、有利には、−40〜+250℃の範囲、好ましくは0〜+150℃の範囲であり、例えば、周囲温度(15〜30℃)に近い温度である。混合は、エチレン下または不活性ガス雰囲気下で行われてよい。 The temperature at which the components of the catalyst composition are mixed is advantageously in the range of −40 to + 250 ° C., preferably in the range of 0 to + 150 ° C., for example, a temperature close to ambient temperature (15 to 30 ° C.). It is. Mixing may be performed under ethylene or under an inert gas atmosphere.
(ダイマー化反応)
本発明の方法は、上記の触媒組成物を用いてエチレンを1−ブテンに選択的にダイマー化させる方法である。
(Dimerization reaction)
The method of the present invention is a method for selectively dimerizing ethylene into 1-butene using the above catalyst composition.
エチレンダイマー化反応は、有利には0.5〜20MPa、好ましくは0.5〜10MPaの全圧下に、20〜180℃、好ましくは40〜140℃の温度で行われる。 The ethylene dimerization reaction is advantageously carried out at a temperature of 20 to 180 ° C., preferably 40 to 140 ° C., under a total pressure of 0.5 to 20 MPa, preferably 0.5 to 10 MPa.
一つの実施形態によると、ダイマー化反応は、バッチ様式で行われる。選択された体積の、上記のように構成された触媒組成物が、有利には溶液中で、通常の撹拌、加熱および冷却の装置を備えた反応器に導入され、次いで、それは、エチレンを用いて、有利には、所望の圧力に加圧され、温度は、好ましくは所望の値に調節される。ダイマー化反応器は、生じた液体の全容積が例えば当初に導入された触媒溶液の容積の2〜50倍を示すまでエチレンを導入することによって一定の圧力に維持される。触媒は、次いで、当業者に知られる通常の手段のいずれかを用いて破壊され、次いで、反応生成物および溶媒は、抜き出され、分離される。 According to one embodiment, the dimerization reaction is performed in a batch mode. A selected volume of the catalyst composition configured as above is introduced, preferably in solution, into a reactor equipped with conventional stirring, heating and cooling devices, which then uses ethylene. Advantageously, it is pressurized to the desired pressure and the temperature is preferably adjusted to the desired value. The dimerization reactor is maintained at a constant pressure by introducing ethylene until the total volume of liquid produced, for example, represents 2 to 50 times the volume of the initially introduced catalyst solution. The catalyst is then destroyed using any conventional means known to those skilled in the art, and then the reaction product and solvent are withdrawn and separated.
別の好ましい実施形態によると、触媒によるエチレンダイマー化反応は、連続的な様式で行われる。第1のバリエーションにおいて、一方のチタン化合物および添加物を含有する溶液と他方のアルミニウム化合物を含有する溶液とは、本発明の触媒組成物が生じるような方法で、エチレンの一定の圧力下に維持された反応器に別々に注入される。前記反応器は、当業者に知られる従来の機械的手段を用いてまたは外部再循環によって撹拌される。温度およびエチレンの圧力は、当業者に知られる従来の手段を用いて所望の値に一定に維持される。反応混合物は、それを一定に維持するための液体レベル調圧弁を用いて抜き出される。触媒は、当業者に知られる任意の通常の手段を用いて連続的に破壊され、次いで、反応から得られた生成物並びに溶媒は、例えば蒸留によって分離される。変換されなかったエチレンは、反応器にリサイクルされてよい。重質フラクションに含まれる触媒の残渣は、焼却されてよい。 According to another preferred embodiment, the catalytic ethylene dimerization reaction is carried out in a continuous manner. In the first variation, the solution containing one titanium compound and additive and the solution containing the other aluminum compound are maintained under a constant pressure of ethylene in such a way that the catalyst composition of the present invention is produced. Are separately injected into the reactor. The reactor is agitated using conventional mechanical means known to those skilled in the art or by external recirculation. The temperature and ethylene pressure are kept constant at the desired values using conventional means known to those skilled in the art. The reaction mixture is withdrawn using a liquid level pressure regulating valve to keep it constant. The catalyst is continuously destroyed using any conventional means known to those skilled in the art, and the product obtained from the reaction as well as the solvent are then separated, for example, by distillation. Unconverted ethylene may be recycled to the reactor. The catalyst residue contained in the heavy fraction may be incinerated.
第2のバリエーションにおいて、一方のチタン化合物および添加物を含有する溶液と他方のアルミニウム化合物とは、本発明の触媒組成物が生じるような方法で第1の反応器/混合機に注入される;前記組成物は、次いで、一定のエチレン圧力下に維持された反応器に連続的に導入される。第1の反応器/混合機中のこの混合物は、不活性雰囲気下にまたはエチレン雰囲気下に生じさせられてよい。反応混合物は、それを一定に維持するための液体レベル調圧弁を用いて抜き出される。触媒は、当業者に知られる任意の通常の手段を用いて連続的に破壊され、次いで、反応から得られた生成物並びに溶媒は、例えば蒸留によって分離される。変換されなかったエチレンは、反応器にリサイクルされてよい。重質フラクションに含まれる触媒の残渣は、焼却されてよい。 In a second variation, the solution containing one titanium compound and additive and the other aluminum compound are injected into the first reactor / mixer in such a way as to produce the catalyst composition of the present invention; The composition is then continuously introduced into a reactor maintained under constant ethylene pressure. This mixture in the first reactor / mixer may be generated under an inert atmosphere or under an ethylene atmosphere. The reaction mixture is withdrawn using a liquid level pressure regulating valve to keep it constant. The catalyst is continuously destroyed using any conventional means known to those skilled in the art, and the product obtained from the reaction as well as the solvent are then separated, for example, by distillation. Unconverted ethylene may be recycled to the reactor. The catalyst residue contained in the heavy fraction may be incinerated.
(得られた生成物)
本発明の方法は、1−ブテンの選択的生産のために用いられ得る。この化合物は、線状の低密度ポリエチレンの製造におけるエチレンとのコモノマーとしての用途のものである。
(Obtained product)
The method of the invention can be used for the selective production of 1-butene. This compound is for use as a comonomer with ethylene in the production of linear low density polyethylene.
以下の実施例は、本発明の範囲を制限することなく本発明を例証する。 The following examples illustrate the invention without limiting the scope of the invention.
(実施例)
(実施例1〜4)
下記表1に提示されるエチレンのダイマー化試験は、有効容積500mLを有するステンレス鋼製オートクレーブにおいて行われた。このオートクレーブは、油の循環によって温度を調節するためのジャケットを備えたものである。撹拌は、機械駆動によるラシュトンインペラーを用いて提供された。
(Example)
(Examples 1-4)
The ethylene dimerization test presented in Table 1 below was conducted in a stainless steel autoclave having an effective volume of 500 mL. This autoclave is provided with a jacket for adjusting the temperature by circulating oil. Agitation was provided using a mechanically driven Rushton impeller.
n−ヘプタン40mL並びにn−ヘプタン中チタン化合物の0.085mol/L溶液5mLが、エチレンの雰囲気下に周囲温度でこの反応器に導入された。一旦、反応器の温度が53℃に達すると、所望量のアルミニウムベースの共触媒(n−ヘプタン5mL中にすでに希釈されている)が、エチレン圧力下に導入された。エチレンの圧力は、23MPaに維持され、温度は、53℃に維持された。1時間の反応の後、エチレンの導入は、停止させられ、反応器は、25℃に冷却された。反応器は、次いで、ガスメータを通じて脱気された。このガスは、気相クロマトグラフィーによって分析された。次いで、反応器に含有される液相が計量され、気相クロマトグラフィーによって分析された。生じたポリマーが回収され、乾燥させられ、計量された。 40 mL of n-heptane as well as 5 mL of a 0.085 mol / L solution of titanium compound in n-heptane were introduced into the reactor at ambient temperature under an atmosphere of ethylene. Once the reactor temperature reached 53 ° C., the desired amount of aluminum-based cocatalyst (already diluted in 5 mL of n-heptane) was introduced under ethylene pressure. The ethylene pressure was maintained at 23 MPa and the temperature was maintained at 53 ° C. After 1 hour of reaction, the ethylene introduction was stopped and the reactor was cooled to 25 ° C. The reactor was then degassed through a gas meter. This gas was analyzed by gas phase chromatography. The liquid phase contained in the reactor was then weighed and analyzed by gas phase chromatography. The resulting polymer was recovered, dried and weighed.
得られた生成物の組成は、下記の表1に与えられる。この表において、活性は、初期に導入されたチタンの重量(グラム)当たりかつ時間当たりの消費されたエチレンの質量として定義される。C4分布(%C4)は、全分布中の4個の炭素原子を含有するオレフィンの量である。百分率%C4 =1は、C4留分中の線状の1−ブテン生成物についての選択性を示す。ポリマーの量(%PE)は、全分布に応じた、回収されたポリマーの質量に相当する。 The composition of the resulting product is given in Table 1 below. In this table, activity is defined as the mass of ethylene consumed per gram of titanium initially introduced and per hour. The C4 distribution (% C 4 ) is the amount of olefin containing 4 carbon atoms in the overall distribution. The percentage% C 4 = 1 indicates the selectivity for the linear 1-butene product in the C 4 fraction. The amount of polymer (% PE) corresponds to the mass of polymer recovered, depending on the overall distribution.
この表において、実施例1および2により、モル比THF/Ti<10を有する組成(比較例(本発明に合致しない))において、モル比AlEt3/Tiを3から6.8に高めることにより、ポリエチレンの生成における相当な増加がもたらされることが示される。 In this table, according to Examples 1 and 2, by increasing the molar ratio AlEt 3 / Ti from 3 to 6.8 in a composition having a molar ratio THF / Ti <10 (comparative example (not in accordance with the invention)) It is shown that there is a considerable increase in the production of polyethylene.
実施例3および4(本発明に合致)により、厳密に10より大きいTHF/Tiモル比を有し、6.8のAlEt3/Ti比を有する組成物(比較例2と比較する)は、エチレンの1−ブテンへの選択的ダイマー化について非常に良好な活性および選択性を有し、かつ、ポリエチレンの生成を伴わないことが実証される。 According to Examples 3 and 4 (according to the invention), a composition having a THF / Ti molar ratio strictly greater than 10 and an AlEt 3 / Ti ratio of 6.8 (compared to Comparative Example 2) It is demonstrated to have very good activity and selectivity for the selective dimerization of ethylene to 1-butene and without the formation of polyethylene.
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CN111408404B (en) * | 2019-01-04 | 2023-03-14 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene |
CN111408403B (en) * | 2019-01-04 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene |
CN111408412B (en) * | 2019-01-04 | 2023-05-09 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization |
CN111408406A (en) * | 2019-01-04 | 2020-07-14 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene |
CN111408411B (en) * | 2019-01-04 | 2024-02-13 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization |
CN111408408B (en) * | 2019-01-04 | 2023-04-11 | 中国石油化工股份有限公司 | Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene |
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US2943125A (en) | 1954-08-07 | 1960-06-28 | Ziegler | Production of dimers and low molecular polymerization products from ethylene |
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GB1312974A (en) | 1969-05-29 | 1973-04-11 | Toyo Soda Mfg Co Ltd | Process and catalyst for dimerization of alpha-olefins |
US3879485A (en) * | 1974-01-25 | 1975-04-22 | Gennady Petrovich Belov | Method of producing butene-1 |
SU681032A1 (en) | 1976-02-23 | 1979-08-25 | Грозненский филиал Охтинского научно-производственного объединения "Пластполимер" | Process for the preparation of dimers and codimers of alpha-olefins |
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